US3787238A - Fluorescent screens - Google Patents

Fluorescent screens Download PDF

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Publication number
US3787238A
US3787238A US00206609A US3787238DA US3787238A US 3787238 A US3787238 A US 3787238A US 00206609 A US00206609 A US 00206609A US 3787238D A US3787238D A US 3787238DA US 3787238 A US3787238 A US 3787238A
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Prior art keywords
block copolymer
screen
polydimethylsiloxane
percent
layer
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Expired - Lifetime
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US00206609A
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English (en)
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P Juliano
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General Electric Co
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General Electric Co
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18Luminescent screens
    • H01J29/28Luminescent screens with protective, conductive or reflective layers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Definitions

  • a fluorescent screen for use as an image intensifying R screen having a support, a light reflecting v layer, a layer of fluorescent particles and an outer pro- [56] Y References cued tective coating.
  • the protective coating is a polymeric UNITED STATES PATENTS material having incorporated therein an effective 2,907,882 10/1915?
  • This invention relates to fluorescent screens for use in radiography and more particularly it relates to protective coatings for X-ray intensifying screens.
  • fluorescent screens or X-ray image intensifying screens are efficient in converting X-ray energy into electro-magnetic radiation within the visible and ultraviolet range. They are usually mounted in pairs in a rigid holder, called a cassette, so that the fluorescent surface of each is in contact with one of the emulsion surfaces of the film.
  • the fluorescent screens have transparent protective coatings such as disclosed by Patten, U.S. Pat. No. 2,907,882.These coatings reduce the abrasion of the active surface and facilitates the removal of dirt and smudge from the screen.
  • the protective coatings such as cellulose derivatives and homopolymers, and complex mixtures of vinyl chloride/vinyl acetate copolymer, poly(methylmethacrylate)v and poly(isobutylmethacrylate).
  • the protective coating should have good abrasion resistance so that the encapsulated phosphor is protected and not easily exposed, hydrophobicity so that water can not permeate into the phosphor layer and react to cause a decreased efficiency, and a low coefficient of friction to minimize the build-up of static charge on the surface during normal use which is capable of damaging the light sensitive film.
  • the frequency with which the screens have to be replaced indicate that the protective coatings used heretofore fail in one or more of the requirements.
  • an improved fluorescent screen comprising a support, a layer of fluorescent particles on said support and an outer protective coating comprised of a hydrophobic, hard film forming polymer having incorporated therein an effective amount of a transparent block copolymer of a polydimethylsilicone and a poly(alkylme.- thacrylate).
  • a light reflecting layer is placed between the support and the fluorescent layer.
  • the novel protective coating is permanent, has good abrasion resistance, is hydrophobic and reduces build-up of static charge.
  • FIG. 1 is a cross sectional view of a fluorescent screen of an embodiment of the present invention
  • FIGS. 2 and 3 are graphic representation illustrating the effect of additions of the novel block copolymer-to the protective layers as a function of their ability to produce nonwetting surfaces.
  • the image intensifying screen 1 is composed of a support 2 as employed in conventional fluorescent screens onto which is usually placed a reflective layer 3. Thereafter a phosphor layer 4 of X-ray fluorescent particles embedded in a filmforming binder is coated on top of the reflective layer 3. The protective coating 5 which is formed from a hard film forming polymer is then applied to the phosphor layer 4.
  • the support 2 is generally composed of paper, metal foil, or plastic sheet.
  • the support is a hydrophobic polymer which includes cellulose derivatives, e.g., cellulose acetate, cellulose acetate butyrate; polyesters, e.g., polyethylene terephthalate; and vinyl polymers, e.g., polyvinyl chloride, polyvinyl acetate, polystyrene, and polyethylene.
  • the thickness of the support may be in the range of about 0.25-30 mils.
  • the reflective layer 3 generally contains a pigment, e.g., magnesium oxide which is embedded in a binder, such as polyvinyl butyral. Typically, the reflective layer 3 has a thickness of about 0.3-1 mils or more.
  • the fluorescent layer 4 contains fluorescent materials which have been used in conventional fluorescent intensifying screens.
  • the layer contains a fluorescent material, such as calcium tungstate, barium sulfate activated with lead, zinc sulfide activated with silver, potassium iodide activated with thallium, etc., together with a binder, such as an organic polymer, e. g., cellulose acetate, polyvinyl acetate, polystyrene, polymethylmethacrylate, polyvinyl butyral, etc.
  • a binder such as an organic polymer, e. g., cellulose acetate, polyvinyl acetate, polystyrene, polymethylmethacrylate, polyvinyl butyral, etc.
  • the surface of the fluorescent layer 41 is protected against moisture and abrasion by applying to it a protective coating 5 of a compatible transparent polymeric composition.
  • the protective coating is a mixture of a polymeric material which includes: clear polyalkylmethacrylate plastics wherein the alkyl group contains from one to four carbon atoms, e.g., polymethyhnethacrylate, polyethylmethacrylate, polypropylmethacrylate and polyisobutylmethacrylate; methylmethacrylate copolymers with other alkylmethacrylates wherein the glass transition temperature (Tg) is in the range of 30100C.; cellulose compounds such as cellulose acetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocelluloses; and polyvinylchloride and vinylchloride vinylacetate copolymers.
  • the binary block copolymer of polydimethylsiloxanepolyalkylmethacrylates are prepared by anionically polymerizing of a cyclopolydimethylsiloxane with a dilithio aromatic initiator, reacting between the resulting lithium terminated polydimethyl siloxane and an alkylmethacrylate, and recovering the polydimethylsiloxane-polyalkylmethacrylate block copolymer from the resulting mixture.
  • the cyclopolydimethylsiloxanes which can be used in the present invention include hexarnethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc. These cyclic siloxanes can be made by hydrolyzing dimethylchlorosilane and separating the resulting cyclic polydimethylsiloxane from the mixture.
  • Some of the alkylmethacrylates which can be employed to produce the polydimethylsiloxane-polyalkylmethacrylate block copolymers are, for example, methylmethacrylate, ethylmethacrylate, butylmethacrylate, etc.
  • the block copolymer can comprise from about 5-90 percent by weight of polydimethylsiloxane blocks and correspondingly from about 10-95 percent by weight of polyalkylmethacrylate blocks.
  • the polydimethylsiloxane blocks may contain from about 3-1 ,500 chemically combined dimethylsiloxane units and preferably from about 3-500 units.
  • the polyalkylmethacrylate blocks can have from l-10,000 chemically combined alkylmethacrylate units and preferably from about SOD-1,500 units.
  • an effective amount of the block copolymer is incorporated into the polymeric plastic material to form the protective coating.
  • the amount of block copolymer incorporated to form the protective coating will vary to some extent with the plastic polymeric material being modified as, for example illustrated by the curves in FIG. 2 and FIG. 3.
  • an effective amount can be as low as 0.001 percent by weight of the plastic polymer material, while for the system using cellulose acetatebutyrate the minimum amount is about 0.5 percent by weight.
  • the maximum amount of block copolymer added should not, however, exceed about percent by weight of the coating composition since greater amounts are unnecessary.
  • the protective coating is applied to the surface of the X-ray image intensifying screen from a coating solution for the polymeric plastic material together with the additive in a suitable solvent.
  • solvents include aromatic solvents, e.g., benzene, toluene and xylene; alcohols, e.g., cyclohexanol; ketones, e.g., acetone, methylethylketone and methylisobutylketone; and esters, e.g., ethyl acetate and butyl acetate.
  • the concentration of polymer plus additive in the solution should be such that there is a sufficient solids content to give a workable viscosity and such that a bubble free film may readily be applied to the under surface.
  • the solution should have a solids content in the range of about l0-20 percent by weight.
  • An opaque light-reflecting layer formulation was prepared by dissolving lOO parts of a low molecular weight poly(methylmethacrylate), m 0.2 in CI-ICI 100 parts of a high molecular weight poly(methylmethacrylate), 17 1.2 in CI-lC1 19.8 parts of a poly(vinylidene chloride) in 620 parts of toluene, 53.5 parts of nbutyl acetate and 116 parts of a l:l(v/v) mixture of ethanol and cyclohexane.
  • the pigment, TiO 540 parts was added and the mixture was roll milled for 24 hours.
  • the suspension was filtered to remove any large TiO- agglomeratives, rolled to remove air bubbles, then cast onto a mil transparent polyethylene terephthalate film to provide a dry film thickness of 1 mil.
  • this opaque light reflecting layer was cast a solution containing the phosphor in a suitable binder/solvent system, such as a plasticized nitrocellulose dissolved in n-butyl acetate.
  • a suitable binder/solvent system such as a plasticized nitrocellulose dissolved in n-butyl acetate.
  • This phosphor layer was cast to provide a dry film having a thickness of about 4 mils.
  • a protective coating layer which was substantially identical to the binder/solvent system for the light reflectin g layer (without the addition of the block copolymer) was cast directly onto the phosphor containing layer.
  • This protective coating layer has a dry film thickness of approximately 0.5 mil.
  • To another identical formulation of binder and solvent was added 0.8 part of a polydimethylsiloxane-polyalkylmethacrylate block copolymer (as described in Example III). This solution was coated onto the surface of the phosphor containing layer of a second screen prepared identically to the first screen.
  • EXAMPLE II An opaque light reflecting layer was prepared by dissolving parts cellulose acetate butyrate in 800 parts of a mixture of ethyl acetate and cellosolve acetate (9:1
  • a phosphor containing layer was prepared using, as a binder, a vinyl acetate-vinyl chloride copolymer dissolved in butyl acetate. The phosphor was dispersed in this solution and applied to the light reflecting layer to produce a phosphor layer with a dry film thickness of about 4 mils.
  • a protective topcoat layer was applied onto the phosphor layer.
  • This topcoat formulation was substantially identical to the binder/solvent system used in the light reflecting layer in this example.
  • To an identical formulation was added 0.5 percent by weight (based on the cellulose acetate butyrate) of a polydimethylsiloxanepolyalkyl-methacrylate block copolymer (as described in Example Ill).
  • Both topcoat formulations were cast onto the phosphor layers of two identical screens to provide dry film thicknesses of about 0.5 mil.
  • the screen containing the block copolymer exhibited a silicone surface upon examination by the water or ethylene glycol contact angle method.
  • the effective limits for the block polymer in this topcoat formulation as well as the acrylic based topcoat are defined in Examples IV and V by simply examining topcoat formulations and the water or ethylene glycol contact angles on the surface of the dry films.
  • EXAMPLE III A substantially transparent polydimethylsiloxanepolymethylmethacrylate block copolymer containing about 34.1 percent by weight of dimethylsiloxy units was prepared using the following procedure.
  • a dilithio initiator was made by stirring for 48 hours at 25C. a mixture of 0.01 mole of benzophenone, 0.05 gram atoms of lithium metal in about 0.5 mole of tetrahydrofuran in a nitrogen atmosphere and under substantially anhydrous conditions.
  • the intrinsic viscosity of the polydimethylsiloxane was found to be about 0.26 when measured in chloroform at 25C., indicating the completion of the hexamethylcyclotrisiloxane polymerizationQThen there was added, with stirring, about 0.1 mole of methylmethacrylate to the mixture over a minute period. The polymerization of the methylmethacrylate was allowed to continue for 2.5 hours while the temperature was maintained at 40C. The lithium ions were neutralized with a sufficient amount of acetic acid,the mixture allowed to warm to room temperature and the product precipitated in methanol.
  • EXAMPLE lV Following the procedure of Example 111, a transparent polydimethylsiloxane-polymethylmethacrylate block copolymer containing about 21.4 percent by weight of polydimethylsiloxane blocks. Various amounts of the block copolymer were incorporated into a cellulose acetate-butyrate polymer (Eastman 171-15). The amount of block copolymer incorporated and the characteristics of the film are shown in the table below:
  • a fluorescent screen comprising a support and a layer of luminescent material bearing a protective layer comprising a transparent film forming polymer having incorporated therein an effective amount of a block copolymer of a polydimethylsilicone and a poly(alkylmethacrylate).
  • the screen of claim 11 having a light reflective layer between the support and the layer of luminescent material.
  • said film forming polymer is a member selected from the group consisting of a polyalkylmethacrylate wherein the alkyl group contains one to four carbon atoms, a methylmethacrylate copolymer with other alkylmethacrylates wherein the glass transition temperature is in the range of 30100C., cellulose acetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, polyvinylchloride and copolymers of vinylchloride and vinylacetate.
  • the block copolymer consists essentially of sequentially arranged blocks of polydimethylsiloxane and polyalkylmethacrylate, wherein the block copolymer is substantially free of homopolymerized polyalkylacrylate and homopolymerized polydimethylsiloxane.
  • the protective layer consists essentially of a polymethylmethacrylate film having incorporated therein 0.01-5.0 percent by weight of the block copolymer.
  • the protective layer consists essentially of a cellulose acetate butyrate polymer having incorporated therein 0.5-5.0 percent by weight of the block copolymer.

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  • Conversion Of X-Rays Into Visible Images (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US00206609A 1971-12-10 1971-12-10 Fluorescent screens Expired - Lifetime US3787238A (en)

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US20660971A 1971-12-10 1971-12-10

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US (1) US3787238A (de)
JP (1) JPS4881495A (de)
BE (1) BE792490A (de)
DE (1) DE2238397A1 (de)
FR (1) FR2164274A5 (de)
GB (1) GB1366404A (de)
NL (1) NL7216758A (de)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028550A (en) * 1975-12-22 1977-06-07 E. I. Du Pont De Nemours And Company X-ray screens
US4205116A (en) * 1977-05-06 1980-05-27 Agfa-Gevaert N.V. Fluorscent X-ray image intensifying screen
US4292107A (en) * 1978-02-10 1981-09-29 Kasei Optonix, Ltd. Process for manufacturing a radiographic intensifying screen
US4478981A (en) * 1982-03-22 1984-10-23 Petrarch Systems Inc. Mixtures of polyacrylate resins and siloxane carbonate copolymers
US4491620A (en) * 1982-09-20 1985-01-01 E. I. Du Pont De Nemours And Company Flexible, nonstaining topcoat for an X-ray intensifying screen
US4550139A (en) * 1982-03-22 1985-10-29 Petrarch Systems, Inc. Mixtures of polyacrylate resins and siloxane-styrene copolymers
US4603260A (en) * 1982-07-21 1986-07-29 Fuji Photo Film Co., Ltd. Composite material for storage of radiation image
US4711827A (en) * 1986-02-24 1987-12-08 E. I. Du Pont De Nemours And Company X-ray intensifying screen with improved topcoat
US4853594A (en) * 1988-08-10 1989-08-01 Rogers Corporation Electroluminescent lamp
US4912333A (en) * 1988-09-12 1990-03-27 Eastman Kodak Company X-ray intensifying screen permitting an improved relationship of imaging speed to sharpness
US5100587A (en) * 1989-11-13 1992-03-31 The United States Of America As Represented By The Department Of Energy Solid-state radioluminescent zeolite-containing composition and light sources
EP1113292A2 (de) * 1999-12-28 2001-07-04 Fuji Photo Film Co., Ltd. Verfahren und Vorrichtung zur Speicherung und Wiedergabe eines Strahlungsbildes
US20050017619A1 (en) * 2003-07-21 2005-01-27 Sheng-Chih Wan Modified high-brightness flat lamp structure
US20050100836A1 (en) * 2003-11-12 2005-05-12 Eastman Kodak Company Phosphor screen and imaging assembly
US20050098738A1 (en) * 2003-11-12 2005-05-12 Eastman Kodak Comapny Phosphor screen and imaging assembly
US20070002584A1 (en) * 2005-06-30 2007-01-04 Jung Ill Cho Backlight unit
EP1770719A2 (de) * 2005-09-30 2007-04-04 Agfa-Gevaert Röntgenbildspeicherschirm mit spezieller Deckschicht zur Verwendung in der Mammografie
WO2008103438A1 (en) * 2007-02-24 2008-08-28 E. I. Du Pont De Nemours And Company Field emission device with anode coating
US20140255700A1 (en) * 2011-11-25 2014-09-11 Lg Chem, Ltd. Resin blend (as amended)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1534154A (en) * 1975-04-15 1978-11-29 Agfa Gevaert Radiographic intensifying screens
JPH0625346B2 (ja) * 1983-12-28 1994-04-06 ソニー株式会社 表示管の製造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2820146A (en) * 1955-02-18 1958-01-14 Du Pont Intensifying screens
US2904689A (en) * 1956-06-01 1959-09-15 United States Radium Corp Fluorescent x-ray screens
US2907882A (en) * 1957-05-03 1959-10-06 Du Pont Fluorescent screens
US2950222A (en) * 1958-05-20 1960-08-23 Jay B Hinson Phosphor bearing surface
US3005103A (en) * 1957-11-12 1961-10-17 Jay B Hinson Phosphors
US3043710A (en) * 1959-02-20 1962-07-10 Du Pont Fluorescent screens
US3164719A (en) * 1961-10-17 1965-01-05 Du Pont Luminescent screen having a protective film
US3502589A (en) * 1965-06-21 1970-03-24 Owens Illinois Inc Cathodoluminescent phosphor-organo-polysiloxane resin compositions
US3663650A (en) * 1970-12-28 1972-05-16 Gen Electric Substantially transparent polydimethylsiloxane - polyalkylmethacrylate compositions and method for making same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2820146A (en) * 1955-02-18 1958-01-14 Du Pont Intensifying screens
US2904689A (en) * 1956-06-01 1959-09-15 United States Radium Corp Fluorescent x-ray screens
US2907882A (en) * 1957-05-03 1959-10-06 Du Pont Fluorescent screens
US3005103A (en) * 1957-11-12 1961-10-17 Jay B Hinson Phosphors
US2950222A (en) * 1958-05-20 1960-08-23 Jay B Hinson Phosphor bearing surface
US3043710A (en) * 1959-02-20 1962-07-10 Du Pont Fluorescent screens
US3164719A (en) * 1961-10-17 1965-01-05 Du Pont Luminescent screen having a protective film
US3502589A (en) * 1965-06-21 1970-03-24 Owens Illinois Inc Cathodoluminescent phosphor-organo-polysiloxane resin compositions
US3663650A (en) * 1970-12-28 1972-05-16 Gen Electric Substantially transparent polydimethylsiloxane - polyalkylmethacrylate compositions and method for making same

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028550A (en) * 1975-12-22 1977-06-07 E. I. Du Pont De Nemours And Company X-ray screens
US4205116A (en) * 1977-05-06 1980-05-27 Agfa-Gevaert N.V. Fluorscent X-ray image intensifying screen
US4292107A (en) * 1978-02-10 1981-09-29 Kasei Optonix, Ltd. Process for manufacturing a radiographic intensifying screen
US4478981A (en) * 1982-03-22 1984-10-23 Petrarch Systems Inc. Mixtures of polyacrylate resins and siloxane carbonate copolymers
US4550139A (en) * 1982-03-22 1985-10-29 Petrarch Systems, Inc. Mixtures of polyacrylate resins and siloxane-styrene copolymers
US4603260A (en) * 1982-07-21 1986-07-29 Fuji Photo Film Co., Ltd. Composite material for storage of radiation image
US4491620A (en) * 1982-09-20 1985-01-01 E. I. Du Pont De Nemours And Company Flexible, nonstaining topcoat for an X-ray intensifying screen
US4711827A (en) * 1986-02-24 1987-12-08 E. I. Du Pont De Nemours And Company X-ray intensifying screen with improved topcoat
US4853594A (en) * 1988-08-10 1989-08-01 Rogers Corporation Electroluminescent lamp
US4912333A (en) * 1988-09-12 1990-03-27 Eastman Kodak Company X-ray intensifying screen permitting an improved relationship of imaging speed to sharpness
US5100587A (en) * 1989-11-13 1992-03-31 The United States Of America As Represented By The Department Of Energy Solid-state radioluminescent zeolite-containing composition and light sources
EP1113292A3 (de) * 1999-12-28 2003-03-12 Fuji Photo Film Co., Ltd. Verfahren und Vorrichtung zur Speicherung und Wiedergabe eines Strahlungsbildes
EP1113292A2 (de) * 1999-12-28 2001-07-04 Fuji Photo Film Co., Ltd. Verfahren und Vorrichtung zur Speicherung und Wiedergabe eines Strahlungsbildes
US6713776B2 (en) 1999-12-28 2004-03-30 Fuji Photo Film Co., Ltd. Method for storing and reproducing radiation image and radiation image storage device
US20050017619A1 (en) * 2003-07-21 2005-01-27 Sheng-Chih Wan Modified high-brightness flat lamp structure
US20050100836A1 (en) * 2003-11-12 2005-05-12 Eastman Kodak Company Phosphor screen and imaging assembly
US20050098738A1 (en) * 2003-11-12 2005-05-12 Eastman Kodak Comapny Phosphor screen and imaging assembly
US7029819B2 (en) 2003-11-12 2006-04-18 Eastman Kodak Company Phosphor screen and imaging assembly
US20070002584A1 (en) * 2005-06-30 2007-01-04 Jung Ill Cho Backlight unit
US7553056B2 (en) * 2005-06-30 2009-06-30 Lg Display Co., Ltd. Backlight unit
EP1770719A2 (de) * 2005-09-30 2007-04-04 Agfa-Gevaert Röntgenbildspeicherschirm mit spezieller Deckschicht zur Verwendung in der Mammografie
EP1770719A3 (de) * 2005-09-30 2008-06-04 Agfa HealthCare NV Röntgenbildspeicherschirm mit spezieller Deckschicht zur Verwendung in der Mammografie
WO2008103438A1 (en) * 2007-02-24 2008-08-28 E. I. Du Pont De Nemours And Company Field emission device with anode coating
US20100072879A1 (en) * 2007-02-24 2010-03-25 E. I. Du Pont De Nemours And Company Field emission device with anode coating
US20140255700A1 (en) * 2011-11-25 2014-09-11 Lg Chem, Ltd. Resin blend (as amended)
US9650510B2 (en) * 2011-11-25 2017-05-16 Lg Chem, Ltd. Resin blend

Also Published As

Publication number Publication date
BE792490A (fr) 1973-03-30
NL7216758A (de) 1973-06-13
FR2164274A5 (de) 1973-07-27
DE2238397A1 (de) 1973-06-20
JPS4881495A (de) 1973-10-31
GB1366404A (en) 1974-09-11

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